Marine biodegradable composition for 3-D printing

ABSTRACT

A composition is provided for producing a 3-D printable material comprised of a marine biodegradable base polymer and a gelling agent in a ratio preselected to achieve a desired rate of degradation of a structure printed from the material. Suitable polymers include polycaprolactone (PCL), polyhydroxyalkanoate (PHA), or polybutylene succinate (PBS). The gelling agent is typically agar. Faster rates of degradation of the structure are obtained with larger proportions of gelling agent in the composition. The composition may also include biological materials to further promote or control the biodegradation of the structure, and other additives such as nutrients for microorganisms or solidifying agents. 3-D printing of the material occurs at relatively lower temperatures to avoid damage to the biological materials.

CROSS REFERENCE TO RELATED APPLICATION

Pursuant to 35 U.S.C. § 120, this nonprovisional patent application is adivisional application claiming the benefit of priority from co-pendingnonprovisional application Ser. No. 15/938,027, having a filing date ofMar. 28, 2018.

STATEMENT OF GOVERNMENT INTEREST

The invention described herein was assigned to the United States Navyand may be used or manufactured by or for the Government of the UnitedStates of America for government purposes without payment of royalties.The invention may be available for licensing for commercial purposes;inquiries should be directed to the Naval Surface Warfare Center PanamaCity Division.

FIELD OF INVENTION

This invention relates to the field of 3-D printing and morespecifically to a marine biodegradable 3-D printing process andcomposition.

BACKGROUND OF THE INVENTION

Unmanned underwater vehicles (UUVs) and other structures or containersare used to house and deliver electronics, sensors, cameras and otherequipment in a marine environment. Often, these structures areexpendable, i.e., they are designed to be used once or continuously overa finite period of time without expectation that they will be retrieved.For example, a housing that contains acoustic sensors and communicationsequipment for monitoring an area of the ocean for a specific period oftime can be dropped in the ocean and left on the sea floor to collectdata during that time and communicate it to the surface. At the end ofthe period for which monitoring is desired, i.e., at the end of itsmission, the housing with its enclosed equipment must be eitherretrieved from the surface, which may be impractical or expensive, orleft behind to degrade in the natural environment over a period of time.However, there is currently no known way to design and produce thesestructures so that their rate of degradation can be controlled.

Furthermore, these vehicles and structures are typically special-purposedevices, rather than mass produced, and may therefore benefit from theefficient fabrication afforded by the 3-D printing processes known inthe art. Currently, modified polylactic acid (PLA),(poly)hydroxybutyrate (PHB), or polyhydroxyalkanoate (PHA) materials aretypically used as biodegradable 3-D printing materials. While thesematerials are biodegradable in a marine environment, the rate ofdegradation of a structure printed from these materials cannot beselected or control. There is an unmet need to produce marinebiodegradable 3-D printable structures for which the rate of degradationof each structure can be selected for a particular mission.

SUMMARY OF THE INVENTION

It is therefore a general purpose and primary object of the presentinvention to provide a composition and method for the 3-D printing of amarine biodegradable structure for which the rate of degradation of thestructure can be controlled. The material can be used for the 3-Dprinting of a UUV, for example, or a portion thereof such as itshousing.

The composition is a 3-D printable material comprised of a biodegradablebase polymer and a gelling agent in a ratio preselected to achieve adesired rate of degradation of a structure printed from the material. Inone embodiment, the base polymer can be Polycaprolactone (PCL),Polyhydroxyalkanoate (PHA), or polybutylene succinate (PBS), and thegelling agent can be agar. PCL, PHA, and PBS are known biodegradablepolymers. Agar is an indigestible polysaccharide that can provide ascaffold support for microorganisms and enzyme materials that candigest, or break down, the polymers. Thus, larger amounts of agar (orother similar gelling agent) in the composition can provide support forlarger amounts of microorganisms and enzyme materials which willconsequently accelerate the degradation of the structure that is printedfrom the composition. The composition is extruded to produce 3-Dprintable filaments. The filaments may then be used in a 3-D printer toform marine biodegradable structures with selected rates of degradationfor specific uses.

In another embodiment, biological materials (e.g., microorganisms,enzymes, etc) may be added to the composition to increase the rate ofdegradation and for a variety of other purposes, such as disablingexplosive devices or growing underwater structures. When thesebiological materials are incorporated into the composition, theextrusion occurs at relatively low temperatures to avoid harming themicroorganisms or other biologicals.

In yet another embodiment, additional additives may be included in thecomposition, such as nutrients to support the growth and activity ofmicroorganisms, antibiotics for microorganism growth selection or growthdeterrence, or certain solidifying agents.

BRIEF DESCRIPTION OF THE DRAWINGS

A more complete understanding of the invention and many of the attendantadvantages thereto will be readily appreciated as the same becomesbetter understood by reference to the following detailed descriptionwhen considered in conjunction with the accompanying drawings whereinlike reference numerals and symbols designate identical or correspondingparts throughout the several views and wherein:

FIGS. 1a, 1b and 1c illustrate an exemplary carrier vehicle constructedby a 3-D printing process using the marine biodegradable material of thepresent invention.

FIG. 2 illustrates an exemplary 3-D printing method for producing amarine biodegradable structure having a selected rate of degradation inthe marine environment.

FIG. 3 provides a table of alternative formulations for marinebiodegradable compositions for given rates of degradation

DETAILED DESCRIPTION OF THE INVENTION

FIGS. 1a, 1b and 1c illustrate an exemplary vehicle (such as a UUV)constructed by a 3-D printing process using the marine biodegradablematerial of the invention at various stages of the degradation cycle. Asdiscussed above, the vehicle may be used to house and transport avariety of materials and equipment, such as sensors, fuel, motors,batteries, explosives, or chemical compounds (collectively referred toherein as the “payload”). In some embodiments, while it is intact thevehicle insulates and protects the payload from the often harsh ambientunderwater environment. When the vehicle degrades, as discussed herein,seawater is able to enter the internal compartments of the vehicle andcome into contact with the payload. In some embodiments, the seawaterwill deactivate payload equipment or materials such as sensors, motors,explosives, etc.

By means of illustration and not limitation, assume that the embodimentshown has a 180-day life cycle. FIG. 1a depicts a vehicle 10 that isintact and ready for deployment, or was recently deployed, in anunderwater environment 20. FIG. 1b indicates the degradation of thevehicle 10 at 90 days at which time the vehicle begins to disintegrate.At this stage, the payload in the interior of the vehicle may come intocontact with the ambient environment 20 and may be deactivated orotherwise start to corrode or degrade. FIG. 1c indicates the degradationof the vehicle at 180 days at which time the vehicle may be completelydisintegrated and its payload is entirely released into the environment20 where it may be deactivated or subject to furthercorrosion/degradation.

FIG. 2 illustrates an exemplary 3-D printing method for producing amarine biodegradable structure having a selected rate of controlleddegradation in the natural environment in accordance with the presentinvention.

In the exemplary method shown, a biodegradable base material is selectedand a selected amount of gelling agent, typically agar, is added to thecomposition. Agar is a natural material of unbranched polysaccharides ofgalactose subunits derived from red algae species and is used in theinstant invention as a gelling agent. It is not typically biodegradable.The rate of erosion of a device manufactured with this compositiondepends upon the percentage of agar in the composition. A higherpercentage of agar results in faster erosion.

In various embodiments, biological materials may be mixed into thecomposition and are released as the structure erodes. Examples ofbiological materials that can be incorporated into the structure includeproteins and enzymes which may be used to disable underwater explosivedevices or biological organisms which may be used to organically growunderwater structures. Microorganisms and/or enzymes may also be addedto speed up the degradation of the structure by feeding on thebiodegradable polymer. The low temperature of the mixing, extrusion and3-D printing processes described herein allows the biological materialsto be included. The higher temperatures required to create structuresusing the previously known 3-D printing processes and compositions wouldkill the biological materials. This is because the 3-D print head mustbe heated enough to extrude the previously known compositions duringprinting. Most biological materials cannot survive in temperatures above120° C. Agar has a melting point of approximately 85° C., allowing it tobe extruded at a temperature safe for the biological materials. Further,it would be preferable to have a base polymer in the composition thathas a melting point similar to that of agar. For example, PLA and PHBhave melting points of 173° C. and 175° C., respectively. At thesetemperatures, agar could “burn” or “scorch” during the extrusionprocess.

Step 1 is the step of selecting a marine biodegradable base polymer. Invarious exemplary embodiments, the preferred base polymer could beeither polycaprolactone (PCL), polyhydroxyalkanoate (PHA), orpolybutylene succinate (PBS).

Polycaprolactone (PCL) is a polyester that degrades due to hydrolysis ofester bonds. PCL has a melting temperature of 60° C., which is close tothe melting temperature of agar and is safe for biological materials.

Polyhydroxyalkanoate (PHA) is a biodegradable polyester that is producedfrom the bacterial fermentation of sugars. The use of wide range ofdifferent starting monomers gives results to PHA products having a rangeof different properties including melting points ranging from 40° C. to180° C.

Polybutylene succinate (PBS) is a biodegradable polyester with similarproperties to polypropylene and a melting temperature equal to 115° C.

In various alternative embodiments, the base polymer selected may benatural or synthetic polymers of polyesters, biopolyesters, proteins,polysaccharides, polyanhydrides, polyamines and polyamides.

Step 2 is the step of adding a controlled amount of gelling agent toproduce a composition consistent with a target rate of degradation. Inthe exemplary embodiment illustrated herein the gelling agent is agar,which is the most common gelling agent used in the preparation ofmicrobiology agar plates or petri dishes and serves as an indigestiblesupport for microorganism growth. However, other gelling agents may beused, including agarose, which could be used to create a more neutrallycharged polymer and has a melting point of 65.5° C. which is similar tothe melting point of PCL (60° C.). In other embodiments, gelatin may beselected as the gelling agent. The gelatin may have a low meltingtemperature of approximately (35° C.) and is digestible to supportmicroorganism growth.

The advantage of including agar (or other gelling agents) in thecomposition is that the agar is an indigestible polysaccharide supportthat can provide scaffold support for microorganisms or enzyme materialsthat are expected to be present in the ambient environment, theadvantages of which are discussed in more detail below. Further,combining agar with the biodegradable polymer selected in Step 1 aboveenables the impregnation of biological microorganisms or enzymes intothe composition prior to or during the 3D printing process.

The ratio of agar to polymer controls the rate of degradation of thecarrier vehicle and, when desired, its payload. Various formulationswithin the scope of the invention may be developed by modifying the basecomposition to achieve a target life span of the vehicle. For example,FIG. 3 illustrates preferred ratios for different desired rates ofdegradation for a specific environment when using PCL as the polymer andagar as the gelling agent. In this example, if a target life of 0-3months is desired, a composition made up of 50%-95% agar, 5%-50% PCL,and up to 1% of biological materials (see discussion of Step 4 below)may be used. If a target life of 3-6 months is desired, a compositionmade up of 25%-50% agar, 50%-75% PCL, and 0.1%-1.0% biologicals may beused. And, if a target life of more than 6 months is desired, acomposition made up of 5%-25% agar and 75%-95% PCL may be used. Similartables may be readily developed for other compositions that includeother polymers and gelling agents. As should be readily apparent tothose skilled in the art, the actual ratios used for desired rates ofdegradation depend on several factors, including the selection of thepolymer and gelling agent, the expected environment in which the carriervehicle would be deployed, as well as the amount of biological materialsthat are incorporated into the composition as discussed below. Otherfactors that may drive the selection of the polymer to agar ratio mayinclude design criteria such as specific rigidity, buoyancy, orstructural strength requirements.

Returning to FIG. 2, Step 3 is the step of incorporating otheringredients. Additives can be included to tailor the composition to meetspecific design requirements of the 3-D printed structure by subtractingmass from either the polymer or the gelling agent and replacing it withthe additives. For example, yeast extract may be added in oneformulation to provide a nutrient-rich, easily available food source formicroorganisms. As an example, the composition could comprise 85%polymer, 5% gelling agent, and 10% yeast extract. Another formulationmay comprise 5% polymer, 85% gelling agent, and 10% yeast extract.Hence, other ingredients can be substituted for a quantity of thegelling agent or polymer based on the desired criteria to alter theproperties (i.e., produce faster or slower degradation relative to thenatural environment). In various embodiments, gel or solidifying agentadditives may be added, including pectin, gelatin, starch, cornstarch,cellulose, collagen, natural or synthetic hagfish slime, polyvinylalcohol, carrageenan or polyethylene glycol. Other ingredients may beadded to the composition, including but not limited to yeast extract,casein hydrosylate, glucose, glycerol, nitrate salts, ammonium salts,amino acids and succinate. Other additives for biological growth andsustainment in a biodegradable material may include gelatin, calciumcarbonate for rigidity, polyethylene glycols (PEG), plasticizer, commonmicroorganism nutrients necessary for growth and antibiotics formicroorganism growth selection or growth deterrence.

Step 4 is the step of incorporating biological materials. The process ofbiodegradation of the carrier vehicle structure is accomplished bymicroorganisms or enzymes which consume, or “feed on,” the biodegradablepolymers that comprise the structure. These biological materials can bepresent in the ambient seawater environment, where they can latch ontothe scaffolding structure provided by the agar or other gelling agent.Additionally, to increase the rate of degradation, selectedmicroorganisms or enzymes may be incorporated into the 3-D printingcomposition of the present invention. The incorporation of thesebiological materials can be used to increase the biodegradation rate ofthe printed polymer-agar blend or serves as an additional scaffold forcementation and sedimentation by microorganisms onto the 3-D printedmaterial. Referring again to FIG. 3, it is shown that a greaterpercentage of biological materials will result in a faster rate ofdegradation. Enzymes and intracellular components can be incorporatedinto the 3-D printed material so that the enzyme thermal stability canbe matched to the polymer blend melting temperature.

The low temperature of the mixing, extrusion, and 3-D printing processallowed by the compositions described herein allows the biologicalmaterials to be included. The temperature may range from 60° C. to 120°C. The higher temperatures required to create the previously knowncompositions would kill the biological materials. Examples of biologicalmaterials that can be incorporated into the structure include enzymessuch as oxidoreductases, lyases, hydrolases, and transferases. Certainenzymes known in the art may be used to disable underwater explosivedevices, or used as biological concrete that can organically growunderwater structures when the carrier vehicle degrades.

In various embodiments, the biological materials may include, but arenot limited to Acetonema, Actinomyces, Alkalibacillus, Ammoniphilus,Amphibacillus, Anaerobacter, Anaerospora, Aneurinibacillus,Anoxybacillus, Bacillus, Brevibacillus, Caldanaerobacter, Caloramator,Caminicella, Cerasibacillus, Clostridium, Clostridiisalibacter,Cohnella, Coxiella, Dendrosporobacter, Desulfotomaculum,Desulfosporomusa, Desulfosporosinus, Desulfovirgula, Desulfunispora,Desulfurispora sp., Filifactor, Filobacillus, Gelria, Geobacillus,Geosporobacter, Gracilibacillus, Halobacillus, Halonatronum,Heliobacterium, Heliophilum, Laceyella, Lentibacillus sp.,Lysinibacillus, Mahella, Metabacterium, Moorella, Natroniella,Oceanobacillus, Orenia, Omithinibacillus, Oxalophagus, Oxobacter,Paenibacillus, Paraliobacillus sp., Pelospora, Pelotomaculum,Piscibacillus, Planifilum, Pontibacillus, Propionispora sp.,Salinibacillus, Salsuginibacillus, Seinonella, Shimazuella,Sporacetigenium, Sporoanaerobacter, Sporobacter, Sporobacterium,Sporohalobacter, Sporolactobacillus sp., Sporomusa, Sporosarcina,Sporotalea, Sporotomaculum, Syntrophomonas, Syntrophospora,Tenuibacillus, Tepidibacter, Terribacillus, Thalassobacillus,Thermoacetogenium, Thermoactinomyces, Thermoalkalibacillus,Thermoanaerobacter, Thermoanaeromonas, Thermobacillus,Thermoflavimicrobium, Thermovenabulum sp., Tuberibacillus, Virgibacillusand Vulcanobacillus sp.

Referring back to FIG. 2, Step 5 is the step of extruding filamentmaterial from the composition of the present invention at a lowtemperature. In one embodiment, the polymer and agar mixtures areblended using an extruder (i.e., single or double screw) at therequisite melting temperature for 10 minutes. The resulting blendedmaterials are extruded at diameters of 1.7 mm-3.0 mm creating 3-Dprintable filaments. However, the diameter may vary depending on the 3-Dprinting approach or printer type employed.

The temperature at which the extrusion occurs depends on the specificmaterials used. For example, when using a composition made up of PCL andagar, the extrusion temperature will be approximately 75° C. In eithercase where biological materials will be incorporated (Step 4), theextrusion temperature will typically be below 120° C. As discussedabove, typical known 3-D printing materials such as PLA have a meltingpoint too high for blending with the agar material or any incorporatedbiological materials. However, using PCL, PHA, and PBS in the basecomposition allows blending of those materials with agar and biologicalsbecause they have a lower melting point that will not result inscorching or burning the agar or destroying the biologicals during theprinting process.

Step 6 is the step of low-temperature 3-D printing using the filamentsextruded from the novel compositions described herein (i.e, in Step 5)and using techniques and equipment known in the art.

Although the invention has been described relative to specificembodiments thereof, there are numerous variations and modificationsthat will be readily apparent to those skilled in the art in light ofthe above teachings. It is therefore to be understood that, within thescope of the appended claims, the invention may be practiced other thanas specifically described.

ratures to avoid damage to the biological materials.

What is claimed as new and desired to be secured by Letters Patent ofthe united States is:
 1. A material for use in the 3-D printing of amarine biodegradable structure, said material comprising: a marinebiodegradable polymer; and a gelling agent.
 2. The material of claim 1,wherein the ratio of said polymer to said gelling agent is selected toachieve a target rate of degradation of the structure.
 3. The materialof claim 2, wherein said polymer material is selected from the groupconsisting of polycaprolactone (PCL), polyhydroxyalkanoate (PHA), orpolybutylene succinate (PBS).
 4. The material of claim 3, wherein saidgelling agent is agar.
 5. The material of claim 3, wherein said gellingagent is selected from the group consisting of agar, agarose, andgelatin.
 6. The material of claim 2, further comprising biologicalmaterials.
 7. The material of claim 6, wherein said biological materialsare capable of consuming said polymer.
 8. The material of claim 7,wherein said biological materials are enzymes.
 9. The material of claim6, wherein said biological materials are selected to provide cementationand sedimentation of microorganisms that are present in a selectedambient environment.
 10. The material of claim 2, further comprisingsolidifying agent additives selected from the group consisting ofpectin, starch, cornstarch, cellulose, collagen, synthetic hagfishslime, polyvinyl alcohol, carrageenan, and polyethylene glycol.
 11. Thematerial of claim 2, further comprising nutrients capable of promotingmicroorganism growth.